EP0699303B1 - Procede et dispositif d'analyse de volumes importants d'echantillons par chromatographie en phase gazeuse - Google Patents

Procede et dispositif d'analyse de volumes importants d'echantillons par chromatographie en phase gazeuse Download PDF

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Publication number
EP0699303B1
EP0699303B1 EP94917652A EP94917652A EP0699303B1 EP 0699303 B1 EP0699303 B1 EP 0699303B1 EP 94917652 A EP94917652 A EP 94917652A EP 94917652 A EP94917652 A EP 94917652A EP 0699303 B1 EP0699303 B1 EP 0699303B1
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Prior art keywords
injector
injection
sample
solvent
valve
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Expired - Lifetime
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EP94917652A
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German (de)
English (en)
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EP0699303A1 (fr
Inventor
Konrad Grob
Fausto Munari
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Thermo Fisher Scientific SpA
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Thermoquest Italia SpA
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation
    • G01N2030/126—Preparation by evaporation evaporating sample
    • G01N2030/127—PTV evaporation

Definitions

  • the present invention relates to a process and a device for gas chromatographic analysis by injecting large volumes of samples containing compounds in traces, i.e. of samples having a small amount of compounds dissolved in a large amount of solvent.
  • the invention relates to the analysis by using splitless injection mode for the compounds dissolved in the solvent, and particularly for injected samples volumes exceeding 5 microliters and separated by using capillary columns.
  • the split mode In the vaporization injection two different injection modes are used : the split mode and the splitless one, namely in absence of splitting.
  • the sample injection is generally performed by means of a syringe.
  • the syringe needle injects the sample through an elastomeric membrane (septum) into a glass liner positioned inside the vaporization chamber.
  • a considerable amount of the whole injected and vaporised sample is eliminated to the atmosphere through the splitting line; this kind of injection is used for relatively concentrated samples in order to avoid to introduce into the capillary gas chromatographic column too large amounts of sample; in the split injection glass liners filled with glass wool or a packing are commonly used.
  • This injection mode implies the transfer into the column of all the vapours of the sample components to be analysed in order to achieve the required sensitivity.
  • the conventional splitless injection takes place at constant temperature, such to allow the vaporization of all sample components, and therefore at a temperature definitely higher than the solvent boiling point.
  • the vapours of the sample components, solvent included, are sent to the column during a preset time period called splitless time. During this period the vapours of the sample compounds are quantitatively transferred to the column.
  • the splitting valve located in the lower portion of the injector
  • the excess of solvent, that has not been transferred into the column is discharged to the atmosphere.
  • the splitless injection is usually performed by using empty glass liners.
  • glass liners with a glass wool cap was mentioned (Wylie et al. - Journal of High Resolution Chromatography 649-655 - Vol. 14, October 1991). According to said publication, the glass wool "seems to reduce discrimination, but can give rise to active sites that enhance the adsorption of polar compounds and catalyse the decomposition of labile molecules".
  • the sample injection is carried out under cold conditions, at a starting temperature below the solvent boiling point and under a flow of carrier gas. Once the injection is performed, the injector body is heated in a programmed way to allow vaporization and transfer to the column the sample components.
  • the solvent is eliminated thanks to the carrier gas through the splitting valve, or in backflush, through another valve (PTV solvent splitting or PTV solvent backflushing).
  • the PTV solvent splitting technique was used for injection of large volumes of sample (solvents) by Vogt et al. J. Chromatogr, 174 (1979) 437 and by Termonia, Leumblez and Munari HRC & CC 11 (1988) 890.
  • the injector vaporization chamber of PTV type, is packed with a suitable material and heated to a starting temperature near the solvent boiling point.
  • the sample injection is performed in temporary absence of carrier gas and in splitless configuration.
  • the carrier gas flow through the vaporizing chamber is reactivated and the chamber temperature is increased to allow vaporization of said components and their passage into the chromatographic colums. During this transfer the vaporising chamber is kept in splitless configuration.
  • a further object of the invention is to provide an injector device for carrying out the above mentioned process.
  • a further object of the present invention is a gaschromatographic injector device according to claim 7.
  • the inert materials are constituted by glass wool or quartz wool treated to make it inert or deactivated, for instance according to the method that will be described hereinbelow.
  • a material that, besides having low thermal mass, has an effect of chromatographic retention on the substances to be analysed, specially at the low temperatures caused by the solvent evaporation is granular poly(para-2,6-diphenylphenylene oxide) (Tenax - AKZO Registered Trademark).
  • the above mentioned liquid intercepting means is used as an alternative to packing material, for stopping the injected liquid sample and retaining it within the vaporization chamber until complete evaporation of the sample.
  • This means may be an insert fitted as a plug of glass or other inert material having a high thermal mass, into the liner. The insert can intercept the passage of liquid but allow the passage of vapours and, when heated will act according to the Leidenfrost phenomenon until the end of solvent vaporization.
  • the injector device comprises in a known way an injector 1, provided with means 1', 18 for heating the same (disclosed in fig. 5), that is connected upstream to a duct 2 for carrier gas feeding and downstream to a capillary column 3.
  • the injector vaporization chamber is provided with a packing 4 that can be made by inerts alone or by inerts provided with stationary phase coating for the retention of the compounds present in the sample. Examples of materials that can be used are glass wool and Tenax (registered trademark).
  • the injector 1 is also connected to vapour discharge means, comprising three-way valve 6 and a first exhaust line 5, called “solvent vapours purge line” having low fluidic resistance and therefore ensuring high flow rates, and to a second purge line 7, i.e. the "septum purge line” having higher fluidic resistance and consequently lower flow rate.
  • the resistance of this line is adjusted by means of a needle valve and is selected so as to insure flow rates of the same order of magnitude as those passing through the column 3.
  • An on-off valve 10 of the needle type is positioned on the second purge line 7 to close it when required.
  • Duct 2 is provided with a valve 8 to cut out the carrier flow to the injector according to the hereunder described procedure.
  • a splitting line 9 also known per se in the art, on which an on/off needle valve 11 is provided.
  • injector 1 is heated up to a temperature sufficient to vaporising and transferring into the GC column the most high-boiling part of the sample to be analyzed (typically 200-350°C). Then the sample injection is started by using a syringe provided with a needle 12 that is introduced into the packing 4 in a position that is a function of the type of solvent used and such as to avoid to introduce liquid sample into'the column 3. Means for sample introduction at programmable speed will be preferably used.
  • the injection is carried out at a speed value that ranges between 10 and 200 ⁇ l/second.
  • the injection speed in this stage is preferably from 10 to 100 ⁇ l/sec.
  • Figure 1 shows the arrangement of valves during the stages of injection and vaporization.
  • the valve 8 has been switched off to cut out the carrier flow to the injector 1
  • the splitting valve 11 is also closed and the valve 6 is switched to connect the injector to purge line 5.
  • the valve 10 can be indifferently in open or closed position, line 7 being in any case cut out by the valve 6.
  • valve 8 is open and the valve 6 is switched in a way to connect the injector 1 to the second purge line 7 having reduced section and high resistance. If the septum purge mode is required, valve 10 is open, otherwise it is closed. The valve 11 is still closed, thus obtaining the classical configuration of splitless mode injection.
  • the compounds of interest are sent to the column 3. Once compounds of interest (that may possibly be only part of those present in the sample) are sent to the column, the valve 11 is switched to the open position, obtaining a splitting configuration (figure 3).
  • Valves 8 and 6 are preferably actuated at a time t (measured from start injection) such that 2 s ⁇ t ⁇ t-splitless where 2s means 2 seconds from the beginning of injection (namely from the introduction of the needle into the injector) and t-splitless corresponds to the time elapsed between the start of the injection and the opening of the splitting line.
  • valves can be synchronous, asynchronous or in another preferred sequence.
  • inerts 4 are required to keep the sample in liquid phase until it evaporates, mainly if said sample has a large volume, as a function of the surface area of the inerts themselves.
  • a preferred inert is a packing of poly(para-2,6-diphenylphenylene oxide) (Tenax - AKZO Registered Trademark).
  • silanised glass or quartz wool e.g. in an amount of about 20-80 mg.
  • this is preferably inactivated, following a process that is similar to that used for the preparation of glass or fused silica capillary columns.
  • the process substantially comprises the following steps:
  • FIG. 5 shows an operative embodiment of an injector for the process according to the invention.
  • Said injector comprises a body 1' of the injector, inside which there is provided a vaporization chamber la defined by an external housing 19 where a calibrated glass tube 20 (glass liner) is inserted, leaving a hollow space 21 for splitting through duct 10', as disclosed hereinafter.
  • An upper sealing gasket 22 closes the hollow space 21.
  • the glass liner 20 has preferably an inner diameter within the range from 2 to 8 mm. Liner 20 is tapered towards the bottom, as indicated by reference 13, for connection to the gas chromatographic capillary column 3, constrained by a blocking insert 14.
  • the vaporization chamber la has a non tapered end that is housed in a small block 15 for distribution of flows and washing of the septum, known per se.
  • the block 15 has a hole in correspondence to said septum 22' that can be pierced for instance by the needle 12 of a known injection syringe 4'. It also has communication ducts in correspondence to carrier gas inlet and purge line outlet.
  • glass liner 20 there is provided glass or quartz wool, deactivated as previously mentioned, or the packing material.
  • vaporization chamber is used to indicate in general the seat where the sample vaporization occurs, in the illustrated example defined by the glass liner 20.
  • body 1' of the injector there are provided different ducts leading to the seat housing the liner that defines the vaporization chamber.
  • Said ducts are a duct 25 to feed carrier gas that is fed at constant pressure.
  • Said duct 25 is provided with a pressure sensor 16 whose function will be described hereinbelow and with an electrovalve for switching off the carrier feed to the ijector.
  • an exhaust line 26 for venting the solvent vapours.
  • Line 26 has, in proximity to its outlet a controlling valve 27, preferably a pneumatic three-way valve.
  • the pneumatic valve 27 has two outlets, one for solvent vapours discharge, or purge, directly connected to atmosphere, and the other for septum purge, connected with a valve 28.
  • This valve has built in a needle valve in series with a pin hole, pneumatically actuated on-off valve.
  • a detector can be installed (e.g. a thermoconductivity detector) to monitor the solvent vaporization process by sensing the variation of solvent vapours in time.
  • a third duct 10' defines a usual splitting line, closed by a valve 11.
  • valve 27 is the three-way valve disclosed in figures 1 to 3 with reference 6.
  • This injector is designed on the basis of a system, known per se, of split-splitless vaporizing with modifications that have the purpose to ensure : a) an appropriate elimination of the solvent vapours through the exhaust line 26 during the solvent vaporization, avoiding the solvent condensation; and b) a monitoring of the evaporation process with indication of the end of the solvent evaporation stage in order to possibly automate the injection procedure.
  • exhaust line 26 should be heated to avoid any condensation of the solvent therein. Said heating is obtained by means of the body 1' of the injector as well as by a special heat conducting body 18 mounted on the upper portion of the injector, the body 18 and body 1' being possibly provided with an insulating lining (not shown).
  • valve 27 as well should be heated at least in its portion near line 26.
  • said valve must guarantee a chemical inertia not altering its characteristics because of the long lasting contact with solvent vapors and must moreover avoid the danger of fire for large quantities of solvent vapours passing therethrough. Therefore pneumatic valves or special electric valves are preferable.
  • line 26 In order to have a suitable elimination of vapours, line 26 must be sufficiently wide (diameter 0.4 mm or more) and short (30 cm or less) not to create a too high fluidic resistance to the solvent that has greater viscosity than that of the carrier gas.
  • the quantity of conveyed heat must be such as to prevent any reduction of the selected temperature. It will therefore be necessary to guarantee the proper amount of heat depending on the selected temperature, the injected quantity, the mass of the injector, the injector speed and the speed of heat transfer to the chamber.
  • an injector body made of aluminium is used with two heating resistors with total capacity preferably exceeding 150 W.
  • the monitoring of the vaporization process can be performed through a suitable detector located on the low fluidic resistance overflow line, downstream valve 27.
  • Said outlet line can be connected in any suitable way to a detector that has the purpose of detecting when the stage of solvent vaporization and the elimination of solvent vapours is over, thus allowing an appropriate timing of the process steps and their automation.
  • valve 27 is switched, so as to connect purge line 26 to valve 28 and the cited high resistance outlet line.
  • the residual solvent vapours present in the purge line are discharged through this line, generally used for septum purge.
  • a detector e.g. a thermoconductivity detector, TCD
  • a second monitoring can be foreseen through the pressure sensor 16.
  • a pressure increase inside the vaporization chamber occurs. Said increase is recorded by the sensor.
  • the end of the solvent vaporization step corresponds to pressure recovering its initial value that is detected by the sensor.
  • a probe (not shown) that detects the temperature of the vaporization chamber or the liner in the zone of the injection, and the increase of said temperature occurring at the end of the solvent vaporization stage.
  • the injector of figure 5 performs the process of the invention in the following way.
  • the system is set at the selected temperature with valve 27 connected to the low fluidic resistance outlet (corresponding to ref. 5 of fig. 1-3) and valves 8 (see fig.1) and 11 closed.
  • the sample is injected in a controlled way as indicated above. If a large sample amount is injected, it is preferable to monitor the solvent evaporation to select the most appropriate time to switch on valve 8 and switch valve 27 to high fluidic restance line and valve 28. In such a case, solvent evaporation is monitored by means of the cited systems (TCD detector and/or pressure sensor 16 and/or temperature probe). In absence of said systems monitoring is carried out in an experimental way.
  • the step of sample transfer begins, preferably after valve 8 is opened and valve 27 is switched to the high resistance line.
  • the transfer time splitless time
  • the transfer time is evaluated in a way similar to the process used in the conventional splitless injection, then opening the splitting valve 11 when the most high-boiling compounds have reached the capillary column.
  • the total splitless (injection) time is equivalent to the solvent vaporization time (t VAP) plus the transfer time under splitless conditions (t TR).
  • on-off valve 8 to avoid penetration of solvent vapours into duct 5, can also be carried out automatically in consequence of the monitoring of said step.
  • Figure 6 shows a modified embodiment of the invention, in which the carrier gas valve 5' can be switched to send a carrier gas flow to a duct 30 connected to the lower portion of the vaporization chamber in order to have said carrier gas moving upwards in a backflushing mode, so as to wash the chamber and sweep away the heavy compounds possibly not to be analysed through GC column.
  • Figure 7 illustrates a chromatogram obtained by injecting a sample of 150 microliters of phenols mixture in water with a concentration of 90-400 pg/ ⁇ l, according to the process of the present invention.
  • Figures 8 and 9 are two chromatograms obtained starting from the above phenol mixture in methylene chloride, injected in 1.2 ⁇ l amount, with concentration of 100-500 pg/ ⁇ l, according to the conventional technique (fig. 8) and in 300 ⁇ l amount, with concentration of 1-5 pg/ ⁇ l according to the technique of the present invention (fig. 9).

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Claims (18)

  1. Procédé pour effectuer une analyse par chromatographie en phase gazeuse en colonnes capillaires, du type comprenant les phases d'injecter à vaporisation un échantillon dans un injecteur (1) contenant du matériel remplissant (4) et chauffé à une température suffisante pour la vaporisation et le transfert complet dans ladite colonne capillaire (3) de la partie la plus haute-bouillante de l'échantillon à analyser; et d'arreter l'alimentation du gaz vecteur(2) audit injecteur; caractérisé en ce qu'il comprend aussi les phases de:
    sélectionner et/ou programmer une vitesse d'injection de l'échantillon dans un intervalle de 10 à 200 µl/sec: effectuer l'injection de l'échantillon à ladite vitesse d'injection pour obtenir un échantillon liquide sur du matériel remplissant inerte (4) ou sur des moyens d'interception de liquide placés dans l'injecteur (1) pendant ladite phase d'injection; décharger les vapeurs obtenues à travers des moyens de décharge de vapeur (5, 6); chauffer la partie supérieure dudit injecteur et au moins une partie desdits moyens de décharge de vapeur; réduire ou couper le débit à travers lesdits moyens de décharge de vapeur (6, 10) et alimenter de nouveau l'injecteur avec ledit gaz vecteur, lorsque l'évaporation du solvant est substantiellement terminée, dans le but de transférer les composés à analyser dudit injecteur (1) à ladite colonne capillaire (3) de l'appareil de chromatographique en phase gazeuse.
  2. Procédé selon la revendication 1, caractérisé en ce que lesdites phases de réduire ou couper le débit à travers lesdits moyens de décharge (5, 6, 7) et d'alimenter de nouveau du gaz vecteur à l'injecteur (1) sont effectuées dans une séquence asynchrone.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'une vitesse variable d'injection est programmée pour prévoir une première phase d'injection de l'échantillon à une vitesse suffisante pour refroidir au moins la zone d'injection dudit échantillon et une deuxième phase d'injection à vitesse constante.
  4. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'une vitesse d'injection constante est choisie et/ou programmée.
  5. Procédé selon l'une quelconque des revendications qui précèdent, caractérisé en ce qu'à la fin du transfert des composés à analyser à ladite colonne (3), ledit injecteur est relié à un conduit de séparation (9) ouvert vers l'atmosphère.
  6. Procédé selon la revendication 5, caractérisé en ce que le débit à travers lesdits moyens de décharge de vapeur est réduit et/ou ledit gaz vecteur est alimenté de nouveau à l'injecteur (1) à un temps t qui correspond à
       2 s < t < t-sans séparation (splitless) où 2s représente deux secondes à partir du début de l'injection et t-splitless est le temps écoulé du début de l'injection jusqu'à l'ouverture du conduit de séparation (9).
  7. Dispositif d'injection pour chromatographie en phase gazeuse pour l'injection d'échantillons ayant des composés dissous dans un solvant liquide, comprenant: une chambre à vaporisation (19-21) fermée par un septum (22') et reliée, du côté opposé, à une colonne pour chromatographie en phase gazeuse (3); des moyens de chauffage (1') pour chauffer ladite chambre; des moyens d'entrée (2, 25) pour alimenter du gaz vecteur à la partie supérieure de ladite chambre; des moyens de décharge de vapeur (5-7, 27) reliés à la partie supérieure de ladite chambre pour décharger les vapeurs dudit solvant et comprenant un conduit de décharge (26); caractérisé en ce qu'il comprend: du matériel remplissant inerte (4) ou des moyens d'interception de liquides, ayant une masse thermique réduite, placés dans ladite chambre à vaporisation; des deuxièmes moyens de chauffage (18) pour chauffer la partie supérieure de l'injecteur, le septum (22') et au moins une partie du conduit de décharge (26) à une température plus élevée que la température de recondensation des vapeurs du solvant; et des moyens pour selectionner et/ou programmer une vitesse d'injection dans un intervalle de 10 à 200 µl/sec.
  8. Injecteur selon la revendication 7, caractérisé en ce que lesdits deuxièmes moyens de chauffage comprennent un bloc (18), fait d'un matériau conducteur de chaleur, en condition d'échange thermique avec au moins la portion la plus longue dudit conduit de décharge (26), avec la partie supérieure de l'injecteur (1) et avec les premiers moyens de chauffage.
  9. Injecteur selon la revendication 8, pourvu d'un revêtement isolant sur la surface extérieure d'au moins un desdits blocs (1', 18) en matériau conducteur de chaleur.
  10. Injecteur selon la revendication 7, caractérisé en ce qu'une vanne de commande à trois voies (27) est reliée audit conduit de décharge (26), ladite vanne étant pourvue de moyens de chauffage pour être chauffée à une température plus élevée que celle de recondensation des vapeurs du solvant, et pourvue d'une première sortie (5) ayant une première résistance aux fluides et d'une deuxième sortie (7) ayant une deuxième résistance aux fluides, ladite deuxième résistance aux fluides étant plus élevée que ladite première résistance aux fluides, l'une ou les deux sorties étant reliables à une source de vide.
  11. Injecteur selon l'une des revendications de 7 à 10, caractérisé en ce que ledit conduit de décharge (26) a un diamètre interne compris entre 0,4 et 2 mm et une longueur de 30 centimètres ou moins.
  12. Injecteur selon l'une des revendications de 7 à 11, caractérisé en ce que la chambre de vaporisation (19, 21) a un diamètre interne compris entre 2 et 8 mm.
  13. Injecteur selon l'une des revendications 7 à 12, comprenant des moyens pour détecter la fin de la phase d'évaporation et de décharge du solvant, choisis parmi un détecteur placé en aval du conduit de décharge, un détecteur de pression (16) placé sur le condit (25) alimentant le gaz vecteur à la chambre de vaporisation et un détecteur de température placé à l'intérieur de la chambre de vaporisation, à côté du point d'injection de l'échantillon.
  14. Injecteur selon la revendication 13, caractérisé en ce que ledit détecteur est un détecteur à conductibilité thermique.
  15. Injecteur selon l'une des revendications 7 à 14, comprenant une vanne (8) pour contrôler l'alimentation du gaz vecteur, agissant sur le conduit correspondant.
  16. Injecteur selon l'une des revendications 7 à 15, caractérisé en ce que lesdits matériaux remplissants inertes (4) sont choisis entre verre désactivé ou laine de quartz et un matériau remplissant ayant un effet de rétention chromatographique.
  17. Injecteur selon la revendication 16, caractérisé en ce que ledit matériau remplissant (4) est du poly(para-2,6-diphénylphénylène oxyde) (Tenax - AKZO marque déposée).
  18. Injecteur selon l'une des revendications 7 à 17, comprenant un conduit de séparation (9, 10') relié à la chambre de vaporisation et contrôlé par une vanne (11) apte à déterminer sa fermeture.
EP94917652A 1993-05-21 1994-05-19 Procede et dispositif d'analyse de volumes importants d'echantillons par chromatographie en phase gazeuse Expired - Lifetime EP0699303B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITMI931058 1993-05-21
ITMI931058A IT1270981B (it) 1993-05-21 1993-05-21 Procedimento e dispositivo per analisi gc capillare di volumi elevati
PCT/EP1994/001624 WO1994028409A2 (fr) 1993-05-21 1994-05-19 Procede et dispositif d'analyse de volumes importants d'echantillons par chromatographie en phase gazeuse

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EP0699303A1 EP0699303A1 (fr) 1996-03-06
EP0699303B1 true EP0699303B1 (fr) 1998-02-18

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Publication number Priority date Publication date Assignee Title
IT1282965B1 (it) * 1996-05-08 1998-04-03 Fisons Instr Spa Procedimento e dispositivo per l'iniezione di campioni liquidi in un gascromatografo.
IT1313986B1 (it) * 1999-10-29 2002-09-26 Thermoquest Italia Spa Iniettore a vaporizzazione
IT1318194B1 (it) 2000-07-19 2003-07-28 Thermoquest Italia Spa Metodo e dispositivo per l'iniezione a vaporizzazione
WO2005040786A2 (fr) 2003-10-23 2005-05-06 Perkinelmer Life And Analytical Sciences Preconcentrateur d'analyte comportant un ecoulement d'adsorption de sortie separe et un ecoulement d'entree de desorption
DE102009003429B3 (de) 2009-02-04 2010-07-01 Joint Analytical Systems Gmbh Vorrichtung und Verfahren zum Aufbereiten von Proben für die Gaschromatografie
US20140331744A1 (en) * 2011-08-11 2014-11-13 Dsm Ip Assets B.V. Sample introduction device and method
US10849600B2 (en) 2016-03-08 2020-12-01 Entech Instruments Inc. Breath condensate and saliva analysis using oral rinse
US10502664B2 (en) 2016-03-08 2019-12-10 Entech Instruments Inc. Vacuum-assisted sample extraction device and method

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Publication number Publication date
DE69408576D1 (de) 1998-03-26
ITMI931058A0 (it) 1993-05-21
WO1994028409A2 (fr) 1994-12-08
ITMI931058A1 (it) 1994-11-21
DE69408576T2 (de) 1999-01-07
WO1994028409A3 (fr) 1994-12-08
EP0699303A1 (fr) 1996-03-06
IT1270981B (it) 1997-05-26

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